Real Gases

Introduction
An ideal gas is a gas having no forces of intermolecular attraction. The gases which follow the
gas laws at all range of pressures and temperatures are considered as ideal gases. An ideal gas
obeys the perfect gas equation Pv = RT and has constant specific heat capacities.
A real gas is a gas having forces of inter molecular attraction. At very low pressure relative to the
critical pressure or at very high temperatures relative to the critical temperature, real gases
behave nearly the same way as a perfect gas. But since at high pressure or at low temperatures
the deviation of real gases from the perfect gas relation is appreciable, these conditions must be
observed carefully, otherwise errors are likely to result from inappropriate application of the
perfect gas laws.
Due to these facts, numerous equations of state for real gas have been developed, the derivation
of which is either analytical, based on the kinetic theory of gases, or empirical, derived from an
experimental data.

Vander Waals Equation of State:

In deriving the equation of state for perfect gases it is assumed that the volume occupied by the
molecules of the gas in comparison to the volume occupied by the gas and the force of attraction
between the adjacent molecules is very small and hence the molecules of gas are neglected. At
low pressures, where the mean free path is large compared to the size of the molecules, these
assumptions are quite reasonable. But at high pressure, where the molecules come close to each
other, these are far from correct. Vander waals equation introduces terms to take into account of
these two modifying factors into the equation of state for a perfect gas.
The Vander Waals equation of state is given by,
a

--- (1)
P v 2 v b RT

RT
a
R = gas constant
or P
2 P = Pressure v = Volume/unit mass
vb v
where a and b are constants for any one gas, which can be determined experimentally, the
constants account for the intermolecular attractions and finite size of the molecules which were
a
assumed to be non-existent in an ideal gas. The term 2 accounts for the intermolecular forces
v
i.e, force of cohesion and the term b was introduced to account for the volume occupied by the
molecules i.e., co-volume.

If the volume of one mole is considered, then the above equation can be written as,
a

P v 2 v b R T

Units P (N/m2), v m 3 / kg mole

R 8314 Nm / kg mol 0 K Or R 0.083143 bar m 3 / kg mol 0 K

a ( Nm 4 / kg mol

b m 3 / kg mol
Determination of Van der Waals constants in terms of critical properties
The determination of two constants a and b in the Van der Waals equation is based on the fact
that the critical isotherm on a p-v diagram has a horizontal inflexion point at the critical point.
Therefore the first and second derivative of P with respect v at the critical point must be zero.
2 p
p
i.e.,
0 and 2
0
v T Tc
v T Tc

From equation (1) we have, P

RT
a
2
vb v

 RT
2a
p

3
2
v
v T v b
2
p
2 RT
6a
and 2
4
3
v
v T v b
At critical points the above equation reduces to
RT

2a
0
v b v 3
2 RT
6a
and
4 0
3
v b v
2

--- (2a)
--- (2b)

Also from equation (1) we have, Pc

RTc
a
2
vb v

--- (2c)

Dividing equation (2a) by equation (2b) and simplifying we get

vc
3
Substituting for b and solving for a from equation (2b) we get
a = 9RTcvc
b

Substituting these expressions for a and b in equation (2c) and solving for v c, we get

3RTc
8 pc
RTc
b
8 pc
vc

and

2 2
27 R Tc
a
64 p c

If the volume of one mole is considered then the above equation can be written as
a

P 2 v b R T
v

Units: P (N/m2), v m3 / kg mol

R =8314 Nm/kg mol0K

m3
kg mole K
b = m3/kg-mol

R 0.083143 bar

a = Nm4 / (kgmol)2 Or bar (m3/kg-mole)2

Note: Usually constants a and b for different gases are given.

Compressibility Factor and Compressibility Chart:

The specific volume of a gas becomes very large when the pressure is low or temperature is high.
Thus it is not possible to conveniently represent the behaviour of real gases at low pressure and
high temperature.
For a perfect gas, the equation of state is Pv = RT. But, for a real gas, a correction factor has to
be introduced in the perfect gas to take into account the deviation of the real gas from the perfect
gas equation. This factor is known as the compressibility factor, Z and is defined as,
Pv
Z
RT
Z = 1 for a perfect gas. For real gases the value of Z is finite and it may be less or more than
unity depending on the temperature and pressure of the gas.
Reduced Properties:
The real gases follow closely the ideal gas equation only at low pressures and high temperatures.
The pressures and temperatures depend on the critical pressure and critical temperature of the
real gases. For example 1000C is a low temperature for most of the gases, but not for air or
nitrogen. Air or nitrogen can be treated as ideal gas at this temperature and atmospheric pressure
with an error which is <1%. This is because nitrogen is well over its critical temperature of
-1470C and away from the saturation region. At this temperature and pressure most of the
substances would exist in solid phase. Hence, the pressure and temperature of a substance is high
or low relative to its critical pressure or temperature.
Gases behave differently at a given pressure and temperature, but they behave very much the
same at temperatures and pressures normalized with respect to their critical temperatures and
pressures. The ratios of pressure, temperature and specific volume of a real gas to the
corresponding critical values are called the reduced properties.
P
T
v
i.e., PR , TR & vR
Pc
Tc
vc
Law of Corresponding states:
This law is used in the approximate determination of the properties of real gases when their
properties at the critical state are known. According to this law, there is a functional relationship
for all substances, which may be expressed mathematically as vR = f (PR,TR). From this law it is
clear that if any two gases have equal values of reduced pressure and reduced temperature, they
will have the same value of reduced volume. This law is most accurate in the vicinity of the
critical point.
Generalized Compressibility Chart:
The compressibility factor of any gas is a function of only two properties, usually temperature
and pressure so that Z1 = f (TR, PR) except near the critical point. This is the basis for the
generalized compressibility chart.
The generalized compressibility chart is plotted with Z versus P R for various values of TR. This is
constructed by plotting the known data of one or more gases and can be used for any gas.
4

It may be seen from the chart that the value of the compressibility factor at the critical state is
about 0.25. Note that the value of Z obtained from Van der waals equation of state at the critical
Pv
3
point, Z c c c which is higher than the actual value.
RTc 8
The following observations can be made from the generalized compressibility chart:
At very low pressures (PR <<1), the gases behave as an ideal gas regardless of
temperature.
At high temperature (TR > 2), ideal gas behaviour can be assumed with good accuracy
regardless of pressure except when (PR >> 1).
The deviation of a gas from ideal gas behaviour is greatest in the vicinity of the critical
point.
The compressibility factor can also be obtained from v-T or v-P data. Since the critical volume
may not be consistent with the generalized chart, the pseudo critical specific volume v c1 is used
in the definition of reduced volume. It is defined by vc1 RTc / Pc . The pseudo reduced volume

v1R is defined as v 1R

vP
v
c
1
vc RTc

Gas
Air
Ammonia
Argon
Carbon dioxide
Carbon monoxide
Freon-12
Helium
Hydrogen
Nitrogen
Oxygen
Sulphurdioxide
Steam

Table: Critical Point Data of Gases

Chemical Pressure Temperature Specific Volume
Formula
Pc bar
Tc K
vc m 3 / kg mole
--37.7
132.8
0.083
NH3
112.8
405.8
0.073
A
44.7
151.0
0.075
CO2
73.8
304.2
0.094
CO
35.0
133.0
0.093
CCl2F2
40.3
385.0
0.215
He
2.3
5.2
0.058
H2
13.0
33.2
0.065
N2
33.9
126.1
0.090
O2
50.6
154.5
0.075
SO2
78.8
430.5
0.0123
H2O
220.9
647.3
0.056

Table: Van Der Waals Constant

Gas
a
b
kN m4/(kg-mol)2 m3/kg-mol
Air
135.8
0.0365
Oxygen
138.0
0.0318
Nitrogen
136.7
0.0386
Water
551.7
0.0304
Methane
228.6
0.0427
Carbon monoxide
147.9
0.0393
Carbon Dioxide
365.6
0.0428
Ammonia
424.9
0.0373
Hydrogen
24.8
0.0266
Helium
3.42
0.0235

Z = pv/RT
0.284
0.29
0.291
0.23
0.29
0.293
0.276
0.242
0.304
0.30

Problems
1. A rigid vessel of volume 0.3 m3 contains 10 kg of air at 3000K. Using (a) the perfect gas
equation, (b) the Vander Walls equation of state and (c) generalized compressibility chart,
determine the pressure which would be exerted by the air on the vessel.
Solution: (a) The perfect gas equation is Pv = RT
RT R T
or P

v
Mv
0 .3
Specific volume of the gas = v
0.03m3 / kg
10
8.3143 x10 3 x300
P
28.67 bar
290.0310 5
a

(b) Vander Waals equation P 2 v b R T

v

2 2
27 R Tc
We have a
64 Pc
From the critical point data of gases, we have Tc = 132.8 K, Pc = 37.7 bar
2
2
27 0.083143 132.8
a
37.7
64
3
a = 1.364 bar (m /kg-mole)2
R Tc 0.083143 x132.8
Also b

8 Pc
8 x37.7
3
= 0.0366m /kg-mole
Substituting the constants a and b in the Van der Waals equation of state, we get

1.364
0.87 0.0366 0.083143x300
P
0.87 2

Noting v = 0.03 m3/kg, v 0.03 x 29 0.87 m 3 / kg mole

0.083143 x300 1.364

28.13 bar
0.87 0.0366 0.87 2
We can also take the values of a and b from Thermodynamic Data Hand Book. [From table C-8
we have a = 135.8 kN m4/(kg-mol)2 and b = 0.0365 m3/kg-mol]

(c) The Pseudo reduced volume, v1R

v Pc
R Tc

0.8737.7
2.97
0.083143132.8
T
300
The reduced temperature, TR

2.26
Tc 132.8
At vR1 = 2.97 & TR = 2.26 from compressibility chart, PR = 0.75

Also since Pc = 37.7 bar,

The pressure exerted by the air on the cylinder P = PR x Pc = 0.75 (37.7) = 28.27 bar
Or
The pressure can also calculated by reading the value of compressibility factor from the chart.
At v1R = 2.97 and TR = 2.26 or TR = 2.26 and PR = 0.75, from the compressibility chart Z = 0.98
ZRT 0.980.289 300
P

28.32 bar
v
1000.03
2. Determine the value of Zcp for the Vander Waals gas
Solution: From the isotherms plotted on P-v diagram it can be seen that the critical isotherm has
an inflection point, whose tangent is horizontal at the critical point.
Pc
2P
0 & 2 0
v cp
v cp
Where cp = critical point.
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We have Vander Waals equation at the critical point,

R Tcp
a
--- (1)
Pcp
2
Vcp b vcp
As Tcp is a constant,

Pcp

vcp

R Tcp

cp

2 R Tcp
2P
6a

4 0
3
2
vcp vcp b vcp

2a
0
vcp3

--- (2)

--- (3)

3
3R T
2R T
xequation(2) equation(3) gives,

0
2
vcp
vcp b 2
vcp vcp b
or

vcp

cp

i.e., vcp 3b

Substitute for b in equation (2),

R Tcp

v 1/ 3v

cp

cp

2a
0
vcp 3

9
a R Tcp vcp
8
Substitute for a & b in equation (1)
9
R Tcp vcp
R Tcp
8
Pcp
2
vcp (1 / 3)vcp
vcp

As

Pcp vcp
R Tcp

Pcp vcp
R Tcp

9
1
8
2
1
3

Z cp , Z cp

3 9

2 8

Z cp

3
8

3. If the values for the reduced pressure and compressibility factor for ethylene are 5 bar and
1.04 respectively, compute the temperature.
Solution: From generated computer chart (from chart 7 in thermodynamic Data Hand Book
compiled by B.T. Nijaguna and B.S. Samaga)
We find for PR = 5 & Z = 1.04,
TR = 2.7
T
But TR
Tc
T = (282.4) (2.7) Since for ethylene Tc = 282.40K
= 762.480K
4. Using the compressibility chart calculate (a) density of N2 at 260 bar & 150C. (b) What
should be the temperature of 1.4 kg of CO2 gas in a container at a pressure of 200 bar to be
have as an ideal gas.

Solution: For N2. from table C-6 (in thermodynamic Data Hand Book compiled by B.T.
Nijaguna and B.S. Samaga) Tc = 125.90K Pc = 33.94
P
260
T
288
PR

7.66, TR

2.29
Pc 33.94
Tc 125.9
From chart 7, for PR = 7.66 & TR = 2.29, Z = 1.08
Pv
P
P
Z

i.e.,
RT RT
ZRT
260 x10 5
Since R = 296.9 J/kg-0K from table C6

1.08296.9 288
= 281.54 kg/m3
(b) For CO2, from table C6, Tc = 3040K, Pc = 73.85 bar.
As the gas behaves like an ideal gas, Z = 1
200
PR
2.71
73.85
From compressibility chart (chart 7), for Z = 1 & PR = 2.71, TR = 2.46
T = Tc TR = 304 (2.46) = 747.840K
5. Find the pressure exerted by methane in a container of capacity 2m3, when it contains 3 kg at
3000K. Using (a) Ideal gas equation (b) Vander Waals equation.
Solution: Molecular weight of methane is McH4 = 16
v
v
2(16)
Molar Volume, v

10.67 m 3 / kg mol
n m
3
M
R 8.3143
Characteristic gas constant, R

0.5196kJ / kg 0 K
M
16
(a) Using ideal gas equation
30.5196 10 3 300
We have, Pv = mRT
P
2.34 bar
2 x10 5
RT
a
(b) We have P
2
v b v
From table C-8, a = 228.6 & b = 0.0427
Substituting in the above equation
8.3143300
228.6
P

232.7 KPa or 2.32 bar

10.67 0.0427 10.67 2
6. Determine the mass of N2 contained in a 30 m3 vessel at 20 MPa and 200 K by using (a) the
ideal gas equation (b) the generalized comp. chart.
(a) Ideal gas equation Pv = mRT
Pv 20 x106 x30
m

10103.07 kg
RT 296.9200
(b) From table C 6 for N2, Pc = 33.94 bar Tc = - 147.10C
= 125.90K

P
20

0.589
Pc 33.94
T
200
TR

1.59
TR 125.9
For PR = 0.589 & TR = 1.59 from chart Z = 0.9
Pv
ZRT
but Z
v
0.00268m3 / kg
RT
P
V
30
m
11194.03kg
v 0.00268
PR

7. The specific volume of CO2 at 1200C is 1.2 m3/kg. Determine the pressure exerted by CO2
using Van der Waals equation. If CO2 is treated as an ideal gas, what should be the pressure
exerted.
v

3
H int : v 1.244 52.8m / kg mol
n

Ans: P = 61.8 KPa

Pid = 61.88 KPa
8. One kg mol of NH3 undergoes a reversible non-flow isothermal compression process and the
volume decreases from 0.2 m3/kg to 0.1 m3/kg, the initial temperature being 450C. If the gas
obeys Van-der-waals equation during the compression process, determine the work done
during the process and final pressure.
Solution: MNH3= 17 v1 0.2(17) 3.4m3 / kg mol , & v2 1.7 m3 / kg mol
We have W1 2 12 Pdv
R T a
2 dv
12
v b v

11
v b
R T ln 2
a

v b
v2 v1
From tables, C 8, a = 424.9 KN-m4/(kg-mol)2
b = 0.0373 m3/kg-mol
W1-2 = - 1737.098 KNm/kg-mole (kJ/kg-mol)
RT
a
Final pressure P2
2 1443.1KPa
v2 b v2
9. Determine the pressure of CO gas having volume of 0.003m3/kg at 164 K with the use of
generalized computer chart. Also determine if the volume of gas is reduced to 80% of the
initial volume, what is the temperature of the gas at the same pressure?
Solution: From table C 6, for CO, Tc = 134.3K, Pc = 34.96 bar
vP
0.003(28)(34.96)
(a) The Pseudo reduced volume, v1R c
0.266
R Tc
0.083143(134.8)
164
From chart 7, for v 1R 0.266 TR
1.234, Z 0.59 & PR 2.6
134.3
Pressure, P = PRPc
10

= 2.6 (34.96)
= 90.81 bar
(b) Volume is reduced to 80% of initial volume, v = 0.8 (0.003) = 0.0024m3/kg
vP
0.0024(28)(34.96)
v1R c
0.213
R Tc
0.083143(134.3)
From chart 7, for vR1 & PR, Z 0.47, TR 1.15
Final temperature is T = TR - Tc
= 152.860K
10. Determine the compressibility factor for O2 at (i) 100 bar, - 700C and (ii) at 5 bar and 300C.
Ans: (i) 0.71
(ii) 0.98
11. Determine the pressure of air at 2050C having a specific volume of 0.00315 m3/kg using (i)
Ideal gas equation and (ii) Van der Waals equation.
Ans: (i) 435.7 bar (ii) 557.3 bar

11